Carboxylate salt or sulfonate salt, and surfactant

ABSTRACT

A carboxylic acid or sulfonic acid salt containing a plurality of carbonyl groups, and a surfactant represented by the following formula: 
       R 1 —C(═O)—R 2 —C(═O)—R 3 -A
 
     wherein R 1 , R 2  and R 3  are as defined herein, and A is —COOX or —SO 3 X, wherein X is H, a metal atom, NR 4   4 , imidazolium optionally containing a substituent, pyridinium optionally containing a substituent, or phosphonium optionally containing a substituent, where R 4 s are each H or an organic group and are the same as or different from each other; and any two of R 1 , R 2 , and R 3  optionally bind to each other to form a ring.

TECHNICAL FIELD

The invention relates to carboxylic acid salts or sulfonic acid salts,and surfactants.

BACKGROUND ART

Patent Literature 1 discloses a processing agent composition for silverhalide photographic sensitive material containing a compound representedby the following formula [A]

wherein R is a hydrogen atom or a hydroxy group; A₁ to A₄ are each—CH₂OH, —COOM₁, or —PO₃M₂M₃, where M₁ to M₃ are each a hydrogen atom, analkali metal, or another cation; and n is an integer of 1 or 2.

CITATION LIST Patent Literature

Patent Literature 1: JP 2003-5329 A

SUMMARY OF INVENTION Technical Problem

The invention aims to provide a novel carboxylic acid salt, or sulfonicacid salt containing a plurality of carbonyl groups, and a surfactant.

Solution to Problem

The invention relates to a compound represented by the followingformula:

wherein

R¹ is a linear or branched alkyl group containing one or more carbonatoms or a cyclic alkyl group containing three or more carbon atoms,with a hydrogen atom that binds to a carbon atom being optionallyreplaced by a hydroxy group or a monovalent organic croup containing anester bond, the alkyl group optionally containing a carbonyl group whencontaining two or more carbon atoms, and the alkyl group optionallycontaining a monovalent or divalent heterocycle or being optionally in acyclized form when containing three or more carbon atoms;

R² and R³ are each individually a single bond or a divalent linkinggroup;

R¹, R², and R³ contain five or more carbon atoms in total;

A is —COOX or —SO₃X, wherein X is H, a metal atom, NR⁴ ₄, imidazoliumoptionally containing a substituent, pyridinium optionally containing asubstituent, or phosphonium optionally containing a substituent, whereR⁴s are each H or an organic group and are the same as or different fromeach other; and

any two of R¹, R², and R³ optionally bind to each other to form a ring.

In the formula, preferably, R² and R³ are each individually a singlebond, a linear or branched alkylene group containing one or more carbonatoms, or a cyclic alkylene group containing three or more carbon atoms,with a hydrogen atom that binds to a carbon atom being optionallyreplaced by a hydroxy group or a monovalent organic group containing anester bond.

In the formula, R¹ is preferably a C1-C8 linear or branched alkyl groupcontaining no carbonyl group, a C3-C8 cyclic alkyl group containing nocarbonyl group, a C2-C45 linear or branched alkyl group containing 1 to10 carbonyl groups, a C3-C45 cyclic alkyl group containing a carbonylgroup, or a C3-C45 alkyl group containing a monovalent or divalentheterocycle.

In the formula, R¹ is preferably a group represented by the followingformula:

wherein n11 is an integer of 0 to 10; R¹¹ is a C1-C5 linear or branchedalkyl group or a C3-C5 cyclic alkyl group; and R¹² is a C0-C3 alkylenegroup, and when n11 is an integer of 2 to 10, R¹²s are the same as ordifferent from each other.

In the formula, preferably, R² and R³ are each individually a linear orbranched alkylene group containing no carbonyl group and containing oneor more carbon atoms.

In the formula, preferably, R² and R³ are each individually a C1-C3linear or branched alkylene group containing no carbonyl group.

In the formula, X is more preferably NH₄.

The invention also relates to a surfactant containing the abovecompound.

The invention also relates to an aqueous dispersant containing the abovecompound.

Advantageous Effects of Invention

The compound of the invention is a compound exhibiting a surfactanteffect, and can suitably be used for anionic surfactants and aqueousdispersants.

DESCRIPTION OF EMBODIMENTS

The invention will be specifically described hereinbelow.

The term “organic group” as used herein means a group containing one ormore carbon atoms or a group obtainable by removing one hydrogen atomfrom an organic compound, unless otherwise mentioned.

Examples of the “organic group” include:

an alkyl group optionally containing one or more substituents,

an alkenyl group optionally containing one or more substituents,

an alkynyl group optionally containing one or more substituents,

a cycloalkyl group optionally containing one or more substituents,

a cycloalkenyl group optionally containing one or more substituents,

a cycloalkadienyl group optionally containing one or more substituents,

an aryl group optionally containing one or more substituents,

an aralkyl group optionally containing one or more substituents,

a non-aromatic heterocyclic group optionally containing one or moresubstituents,

a heteroaryl group optionally containing one or more substituents,

a cyano group,

a formyl group,

RaO—,

RaCO—,

RaSO₂—,

RaCOO—,

RaNRaCO—,

RaCONRa—,

RaSO₂NRa—,

RaNRaSO₂—,

RaOCO—, and

RaOSO₂—,

wherein each Ra is independently

an alkyl group optionally containing one or more substituents,

an alkenyl group optionally containing one or more substituents,

an alkynyl group optionally containing one or more substituents,

a cycloalkyl group optionally containing one or more substituents,

a cycloalkenyl group optionally containing one or more substituents,

a cycloalkadienyl group optionally containing one or more substituents,

an aryl group optionally containing one or more substituents,

an aralkyl group optionally containing one or more substituents,

a non-aromatic heterocyclic group optionally containing one or moresubstituents, or

a heteroaryl group optionally containing one or more substituents.

The organic group is preferably an alkyl group optionally containing oneor more substituents.

The term “substituent” as used herein means a group which can replaceanother atom or a group, unless otherwise mentioned. Examples of the“substituent” include an aliphatic group, an aromatic group, aheterocyclic group, an acyl group, an acyloxy group, an acylamino group,an aliphatic oxy group, an aromatic oxy group, a heterocyclic oxy group,an aliphatic oxycarbonyl group, an aromatic oxycarbonyl group, aheterocyclic oxycarbonyl group, a carbamoyl group, an aliphatic sulfonylgroup, an aromatic sulfonyl group, a heterocyclic sulfonyl group, analiphatic sulfonyloxy group, an aromatic sulfonyloxy group, aheterocyclic sulfonyloxy group, a sulfamoyl group, an aliphaticsulfonamide group, an aromatic sulfonamide group, a heterocyclicsulfonamide group, an amino group, an aliphatic amino group, an aromaticamino group, a heterocyclic amino group, an aliphatic oxycarbonylaminogroup, an aromatic oxycarbonylamino group, a heterocyclicoxycarbonylamino group, an aliphatic sulfinyl group, an aromaticsulfinyl group, an aliphatic thio group, an aromatic thio group, ahydroxy group, a cyano group, a sulfa group, a carboxy group, analiphatic oxyamino group, an aromatic oxyamino group, a carbamoylaminogroup, a sulfamoyl amino group, a halogen atom, a sulfamoyl, and adiaromatic oxyphosphinyl group.

The aliphatic group may be either saturated or unsaturated, and maycontain any of a hydroxy group, an aliphatic oxy group, a carbamoylgroup, an aliphatic oxycarbonyl group, an aliphatic thio group, an aminogroup, an aliphatic amino group, an acylamino group, a carbamoylaminogroup, and the like. Examples of the aliphatic group include alkylgroups containing one to eight, preferably one to four carbon atoms intotal, such as a methyl group, an ethyl group, a vinyl group, acyclohexyl group, and a carbamoylmethyl group.

The aromatic group may contain any of a nitro group, a halogen atom, analiphatic oxy group, a carbamoyl group, an aliphatic oxycarbonyl group,an aliphatic thio group, an amino group, an aliphatic amino group, anacylamino group, a carbamoylamino group, and the like. Examples of thearomatic group include aryl groups containing six to twelve, preferablysix to ten carbon atoms in total, such as a phenyl group, a4-nitrophenyl group, a 4-acetylaminophenyl group, and a4-methanesulfonylphenyl group.

The heterocyclic group may contain any of a halogen atom, a hydroxygroup, an aliphatic oxy group, a carbamoyl group, an aliphaticoxycarbonyl group, an aliphatic thio group, an amino group, an aliphaticamino group, an acylamino group, a carbamoylamino group, and the like.Examples of the heterocyclic group include 5- or 6-membered heterocyclicgroups containing two to twelve, preferably two to ten carbon atoms intotal, such as a 2-tetrahydrofuryl group and a 2-pyrimidyl group.

The acyl group may contain any of an aliphatic carbonyl group, anarylcarbonyl group, a heterocyclic carbonyl group, a hydroxy group, ahalogen atom, an aromatic group, an aliphatic oxy group, a, carbamoylgroup, an aliphatic oxycarbonyl group, an aliphatic thio group, an aminogroup, an aliphatic amino group, an acylamino group, a carbamoylaminogroup, and the like. Examples of the acyl group include acyl groupscontaining two to eight, preferably two to four carbon atoms in total,such as an acetyl group, a propanoyl group, a benzoyl group, and a3-pyridinecarbonyl group.

The acylamino group may contain any of an aliphatic group, an aromaticgroup, a heterocyclic group, and the like, and may contain any of anacetylamino group, a benzoylamino group, a 2-pyridinecarbonylaminogroup, a propanoylamino group, and the like, for example. Examples ofthe acylamino group include acylamino groups containing two to twelve,preferably two to eight carbon atoms in total, and alkylcarbonylaminogroups containing two to eight carbon atom in total, such as anacetylamino group, a benzoylamino group, a 2-pyridinecarbonylaminogroup, and a propanoylamino group.

The aliphatic oxycarbonyl group may be either saturated or unsaturated,and may contain any of a hydroxy group, an aliphatic oxy group, acarbamoyl group, an aliphatic oxycarbonyl group, an aliphatic thiogroup, an amino group, an aliphatic amino group, an acylamino group, acarbamoylamino group, and the like. Examples of the aliphaticoxycarbonyl group include alkoxycarbonyl groups containing two to eight,preferably two to four carbon atoms in total, such as a methoxycarbonylgroup, an ethoxycarbonyl group, and a (t)-butoxycarbonyl group.

The carbamoyl group may contain any of an aliphatic group, an aromaticgroup, a heterocyclic group, and the like. Examples of the carbamoylgroup include an unsubstituted carbamoyl group and alkylcarbamoyl groupscontaining two to nine carbon atoms in total, preferably anunsubstituted carbamoyl group and alkylcarbamoyl groups containing twoto five carbon atoms in total, such as a N-methylcarbamoyl group, aN,N-dimethylcarbamoyl group, and a N-phenylcarbamoyl group.

The aliphatic sulfonyl group may be either saturated or unsaturated, andmay contain any of a hydroxy group, an aromatic group, an aliphatic oxygroup, a carbamoyl group, an aliphatic oxycarbonyl group, an aliphaticthio group, an amino group, an aliphatic amino group, an acylaminogroup, a carbamoylamino group, and the like. Examples of the aliphaticsulfonyl group include alkyl sulfonyl groups containing one to six,preferably one to four carbon atoms in total, such as a methanesulfonylgroup.

The aromatic sulfonyl group may contain any of a hydroxy group, analiphatic group, an aliphatic oxy group, a carbamoyl group, an aliphaticoxycarbonyl group, an aliphatic thio group, an amino group, an aliphaticamino group, an acylamino group, a carbamoylamino group, and the like.Examples of the aromatic sulfonyl group include arylsulfonyl groupscontaining six to ten carbon atoms in total, such as a benzenesulfonylgroup.

The amino group may contain any of an aliphatic group, an aromaticgroup, a heterocyclic group, and the like.

The acylamino group may contain any of an acetylamino group, abenzoylamino group, a 2-pyridinecarbonylamino group, a propanoylaminogroup, and the like. Examples of the acylamino group include acylaminogroups containing two to twelve, preferably two to eight carbon atoms intotal, more preferably alkylcarbonylamino groups containing two to eightcarbon atoms in total, such as an acetylamino group, a benzoylaminogroup, a 2-pyridinecarbonylamino group, and a propanoylamino group.

The aliphatic sulfonamide group, the aromatic sulfonamide group, and theheterocyclic sulfonamide group may respectively be a methanesulfonamidegroup, a benzene sulfonamide group, and a 2-pyridinesulfonamide group,for example.

The sulfamoyl group may contain any of an aliphatic group, an aromaticgroup, a heterocyclic group, and the like. Examples of the sulfamoylgroup include a sulfamoyl group, alkylsulfamoyl groups containing one tonine carbon atoms in total, dialkylsulfamoyl groups containing two toten carbon atoms in total, arylsulfamoyl groups containing seven tothirteen carbon atoms in total, and heterocyclic sulfamoyl groupscontaining two to twelve carbon atoms in total, more preferably asulfamoyl group, alkylsulfamoyl groups containing one to seven carbonatoms in total, dialkylsulfamoyl groups containing three to sax carbonatoms in total, arylsulfamoyl groups containing six to eleven carbonatoms in total, and heterocyclic sulfamoyl groups containing two to tencarbon atoms in total, such as a sulfamoyl group, a methylsulfamoylgroup, a N,N-dimethylsulfamoyl group, a phenylsulfamoyl group, and a4-pyridinesulfamoyl group.

The aliphatic oxy group may be either saturated or unsaturated, and maycontain any of a methoxy group, an ethoxy group, an i-propyloxy group, acyclohexyloxy group, a methoxyethoxy group, and the like. Examples ofthe aliphatic oxy group include alkoxy groups containing one to eight,preferably one to six carbon atoms in total, such as a methoxy group, anethoxy group, an i-propyloxy group, a cyclohexyloxy group, and amethoxyethoxy group.

The aromatic amino group and the heterocyclic amino group each maycontain any of an aliphatic group, an aliphatic oxy group, a halogenatom, a carbamoyl group, a heterocyclic group ring-fused with the arylgroup, and an aliphatic oxycarbonyl group, preferably any of analiphatic group containing one to four carbon atoms in total, analiphatic oxy group containing one to four carbon atoms in total, ahalogen atom, a carbamoyl group containing one to four carbon atoms intotal, a nitro group, and an aliphatic oxycarbonyl group containing twoto four carbon atoms in total.

The aliphatic thio group may be either saturated or unsaturated, andexamples thereof include alkylthio groups containing one to eight, morepreferably one to six carbon atoms in total, such as a methylthio group,an ethylthio group, a carbamoylmethylthio group, and a t-butylthiogroup.

The carbamoylamino group may contain any of an aliphatic group, an arylgroup, a heterocyclic group, and the like. Examples of thecarbamoylamino group include a carbamoylamino group, alkylcarbamoylaminogroups containing two to nine carbon atoms in total,dialkylcarbamoylamino groups containing three to ten carbon atoms intotal, arylcarbamoylamino groups containing seven to thirteen carbonatoms in total, and heterocyclic carbamoylamino groups containing threeto twelve carbon atoms in total, preferably a carbamoylamino group,alkylcarbamoylamino groups containing two to seven carbon atoms intotal, dialkylcarbamoylamino groups containing three to six carbon atomsin total, arylcarbamoylamino groups containing seven to eleven carbonatoms in total, and heterocyclic carbamoylamino group containing threeto ten carbon atoms in total, such as a carbamoylamino group, amethylcarbamoylamino group, a N,N-dimethylcarbamoylamino group, aphenylcarbamoylamino group, and a 4-pyridinecarbamoylamino group.

The invention relates to a compound represented by the followingformula.

In the formula, R¹ is a linear or branched alkyl group containing one ormore carbon atoms or a cyclic alkyl group containing three or morecarbon atoms.

The alkyl group, when containing three or more carbon atoms, mayoptionally contain a carbonyl group (—C(═O)—) between two carbon atoms.The alkyl group, when containing two or more carbon atoms, mayoptionally contain a carbonyl group at an end of the alkyl group. Inother words, acyl groups such as an acetyl group represented byCH₃—C(═O)— are also included in the alkyl group.

The alkyl group, when containing three or more carbon atoms, mayoptionally contain a monovalent or divalent heterocycle, or mayoptionally be in a cyclized form. The heterocycle is preferably anunsaturated heterocycle, more preferably an oxygen-containingunsaturated heterocycle, and may be a furan ring, for example. In R¹, adivalent heterocycle may be inserted between two carbon atoms, or adivalent heterocycle may be present at an end and bind to —C(═O)—, or amonovalent heterocycle may be present at an end of the alkyl group.

The “number of carbon atoms” in the alkyl group herein includes thenumber of carbon atoms constituting the carbonyl groups and the numberof carbon atoms constituting the heterocycles. For example, the numberof carbon atoms in the group represented by CH₃—C(—O)—CH₂— is 3, thenumber of carbon atoms in the group represented byCH₃—C(═O)—O₂H₄—C(═O)—C₂H₄— is 7, and the number of carbon atoms in thegroup represented by CH₃—C(═O)— is 2,

The alkyl group for R¹ may optionally contain a substituent. Thesubstituent which may be contained in the alkyl group for R¹ ispreferably a halogen atom, a C1-C10 linear or branched alkyl group, aC3-C10 cyclic alkyl group, or a hydroxy group, particularly preferably amethyl group or an ethyl group.

In the alkyl group, a hydrogen atom that binds to a carbon atom mayoptionally be replaced by a functional group such as a hydroxy group(—OH) or a monovalent organic group containing an ester bond. Still, itis preferably not replaced by any functional group.

An example of the monovalent organic group containing an ester bond is agroup represented by the formula: —O—C(═O)—R¹⁰¹, wherein R¹⁰¹ is analkyl group.

In the formula, R² and R³ are each individually a single bond or adivalent linking group.

Preferably, R² and R³ are each individually a single bond, a linear orbranched alkylene group containing one or more carbon atoms, or a cyclicalkylene group containing three or more carbon atoms.

The alkylene group constituting R² and R³ preferably contains nocarbonyl group.

In the alkylene group, a hydrogen atom that binds to a carbon atom mayoptionally be replaced by a functional group such as a hydroxy group(—OH) or a monovalent organic group containing an ester bond. Still, itis preferably not replaced by any functional group.

An example of the monovalent organic group containing an ester bond is agroup represented by the formula: —O—C(═O)—R¹⁰², wherein R¹⁰² is analkyl group.

In the alkylene group, 75% or less of the hydrogen atoms binding to anycarbon atom may be replaced by halogen atoms, 50% or less thereof may bereplaced by halogen atoms, or 25% or less thereof may be replaced byhalogen atoms. The alkylene group is preferably a non-halogenatedalkylene group containing no halogen atoms such as fluorine atoms andchlorine atoms.

R¹, R², and R³ contain 5 or more carbon atoms in total. The total numberof carbon atoms is preferably 7 or greater, more preferably 9 orgreater, while preferably 20 or smaller, more preferably 18 or smaller,still more preferably 15 or smaller.

Any two of R¹, R², and R³ may optionally bind to each other to form aring.

In the formula, A is —COOX or —SO₃X, wherein X is H, a metal atom, NR⁴₄, imidazolium optionally containing a substituent, pyridiniumoptionally containing a substituent, or phosphonium optionallycontaining a substituent, wherein R⁴ is H or an organic group, and thefour R⁴s are the same as or different from each other. The compound ofthe invention is preferably a carboxylic acid salt or a sulfonic acidsalt.

Examples of the metal atom include alkali metals (Group 1) and alkalineearth metals (Group 2), and Na, K, or Li is preferred.

R⁴ is preferably H or a C1-C10 organic group, more preferably H or aC1-C4 organic group. Examples of the metal atom include alkali metals(Group 1) and alkaline earth metals (Group 2), and Na, K, or Li ispreferred.

X is preferably H, a metal atom, or NR⁴ ₄, more preferably H, an alkalimetal (Group 1), an alkaline earth metal (Group 2), or NR⁴ ₄, still morepreferably H, Na, K, Li, or NH₄, further more preferably Na, K, or NH₄,particularly preferably Na or NH₄, most preferably NH₄.

In the formula, R¹ is preferably a C1-C8 linear or branched alkyl groupcontaining no carbonyl group, a C3-C8 cyclic alkyl group containing nocarbonyl group, a C2-C45 linear or branched alkyl group containing 1 to10 carbonyl groups, a C3-C45 cyclic alkyl group containing a carbonylgroup, or a C3-C45 alkyl group containing a monovalent or divalentheterocycle.

R¹ is more preferably a group represented by the following formula:

wherein n11 is an integer of 0 to 10; R¹¹ is a C1-C5 linear or branchedalkyl group or a C3-C5 cyclic alkyl group; and R¹² is a C0-C3 alkylenegroup, and when n11 is an integer of 2 to 10, R¹²s may be the same as ordifferent from each other.

In the formula, n11 is preferably an integer of 0 to 5, more preferablyan integer of 0 to 3, still more preferably an integer of 1 to 3.

The alkyl group for R¹¹ preferably contains no carbonyl group.

In the alkyl group for R¹¹, a hydrogen atom that binds to a carbon atommay optionally be replaced by a functional group such as a hydroxy group(—OH) or a monovalent organic group containing an ester bond. Still, itis preferably not replaced by any functional group.

An example of the monovalent organic group containing an ester bond is agroup represented by the formula: —O—C(═O)—R¹⁰³, wherein R¹⁰³ is analkyl group.

In the alkyl group for R¹¹, 75% or less of the hydrogen atoms binding toany carbon atom may be replaced by halogen atoms, 50% or less thereofmay be replaced by halogen atoms, or 25% or less thereof may be replacedby halogen atoms. The alkyl group is preferably a non-halogenated alkylgroup containing no halogen atoms such as fluorine atoms and chlorineatoms. The alkyl group for R¹¹ may contain 1 to 20 carbon atoms. Thenumber of carbon atoms is preferably 1 to 15, more preferably 1 to 12,still more preferably 1 to 10, further more preferably 1 to 8, stillfurther more preferably 1 to 6, still much more preferably 1 to 3,particularly preferably 1 or 2, most preferably 1. The alkyl group forR¹¹ preferably consists only of any of primary carbons, secondarycarbons, and tertiary carbons, particularly preferably consists of anyof primary carbons and secondary carbons. In other words, R¹¹ ispreferably a methyl group, an ethyl group, a n-propyl group, or anisopropyl group, most preferably a methyl group.

R¹¹ is preferably a C1-C10 linear or branched alkyl group optionallycontaining a substituent or a C3-C10 cyclic alkyl group optionallycontaining a substituent, more preferably a C1-C10 linear or branchedalkyl group containing no carbonyl group or a C3-C10 cyclic alkyl groupcontaining no carbonyl group, still more preferably a C1-C10 linear orbranched alkyl group containing no substituent, further more preferablya C1-C3 linear or branched alkyl group containing no substituent,particularly preferably a methyl group (—CH₃) or an ethyl group (—C₂H₅),most preferably a methyl group (—CH₃).

R¹² is a C0-C3 alkylene group. The number of carbon atoms is preferably1 to 3.

The alkylene group for R¹² may be either linear or branched.

The alkylene group for R¹² preferably contains no carbonyl group. R¹² ismore preferably an ethylene group (—C₂H₄—) or a propylene group(—C₃H₆—).

In the alkylene group for R¹², a hydrogen atom that binds to a carbonatom may optionally be replaced by a functional group such as a hydroxygroup (—OH) or a monovalent organic group containing an ester bond.Still, it is preferably not replaced by any functional group.

An example of the monovalent organic group containing an ester bond is agroup represented by the formula: —O—C(═O)—R¹⁰⁴, wherein R¹⁰⁴ is analkyl group.

In the alkylene group for R¹², 75% or less of the hydrogen atoms bindingto any carbon atom may be replaced by halogen atoms, 50% or less thereofmay be replaced by halogen atoms, or 25% or less thereof may be replacedby halogen atoms. The alkylene group is preferably a non-halogenatedalkylene group containing no halogen atoms such as fluorine atoms andchlorine atoms.

Preferably, R² and R³ are each individually a linear or branchedalkylene group containing no carbonyl group and containing one or morecarbon atoms, more preferably a C1-C3 linear or branched alkylene groupcontaining no carbonyl group, still more preferably an ethylene group(—C₂H₄—) or a propylene group (—C₃H₆—).

Examples of the above compound include the following compounds. In eachformula, A is defined as mentioned above.

The compound of the invention may favorably be produced by a productionmethod including:

a step (11) of reacting a compound (10) represented by the followingformula:

(wherein R³ is defined as mentioned above; and E is a leaving group),lithium, and a chlorosilane compound represented by the formula: R²⁰¹₃Si—Cl (wherein R²⁰¹s are each individually an alkyl group or an arylgroup) to provide a compound (11) represented by the following formula:

(wherein R³, R²⁰¹, and E are defined as mentioned above);

a step (12) of reacting the compound (11) and an olefin represented bythe following formula:

(wherein R¹ is defined as mentioned above; and R²¹ is a single bond or adivalent linking group) to provide a compound (12) represented by thefollowing formula:

(wherein R¹, R²¹, R³, and E are defined as mentioned above);

a step (13) of eliminating the leaving group contained in the compound(12) to provide a compound (13) represented by the following formula:

(wherein R¹, R²¹, and R³ are defined as mentioned above);

a step (14) of oxidizing the compound (13) to provide a compound (14)represented by the following formula:

(wherein R¹, R²¹, and R³ are defined as mentioned above); and

a step (15) of bringing the compound (14) to be in contact with analkali to provide a compound (15) represented by the following formula:

(wherein R¹, R²¹, R³, and X are defined as mentioned above).

When R¹ contains a furan ring, the furan ring may be cleaved with anacid and converted into a dicarbonyl derivative, for example. Examplesof the acid include acetic acid, hydrochloric acid, andp-toluenesulfonic acid. Acetic acid is preferred.

In the step (11), the compound (11) is preferably obtained by reactinglithium and the chlorosilane compound in advance to provide asiloxylithium compound, and then reacting this siloxylithium compoundand the compound (10).

E represents a leaving group. Examples of the leaving group include atert-butyldimethylsilyl (TBS) group, a triethylsilyl (TES) group, atriisopropylsilyl (TIPS) group, a tert-butyldiphenylsilyl (TBDPS) group,and a benzyl (Bn) group.

R²¹ is preferably a single bond or a linear or branched alkylene groupcontaining one or more carbon atoms.

Examples of the chlorosilane compound include the following.

Any of the reactions in the step (11) may be performed in a solvent. Thesolvent is preferably an organic solvent, more preferably an aproticpolar solvent, still more preferably an ether. Examples of the etherinclude ethyl methyl ether, diethyl ether, monoglyme(ethylene glycoldimethyl ether), diglyme(diethylene glycol dimethyl ether),triglyme(triethylene glycol dimethyl ether), tetrahydrofuran,tetraglyme(tetraethylene glycol dimethyl ether), and crown ethers (e.g.,15-crown-5, 18-crown-6). Tetrahydrofuran and diethyl ether arepreferred.

The temperature of the reaction between lithium and the chlorosilanecompound in the step (11) is preferably −78° C. to 150° C., morepreferably −78° C. to 100° C., still more preferably 0° C. to 100° C.,particularly preferably 10° C. to 40° C.

The temperature of the reaction between the siloxylithium compound andthe compound (10) in the step (11) is preferably −100° C. to 0° C., morepreferably −80° C. to −50° C., while preferably −100° C. to 100° C.,more preferably −80° C. to 50° C.

The pressure of the reaction between lithium and the chlorosilanecompound in the step (11) is preferably 0.1 to 5 MPa, more preferably0.1 to 1 MPa.

The pressure of the reaction between the siloxylithium compound and thecompound (10) in the step (11) is preferably 0.1 to 5 MPa, morepreferably 0.1 to 1 MPa.

The duration of the reaction between lithium and the chlorosilanecompound in the step (11) is preferably 0.1 to 72 hours, more preferably1 to 48 hours, still more preferably 6 to 10 hours.

The duration of the reaction between the siloxylithium compound and thecompound (10) in the step (11) is preferably 0.1 to 72 hours, morepreferably 1 to 48 hours, still more preferably 1 to 2 hours.

For the reaction ratio between the compound (11) and the olefin in thestep (12), the amount of the olefin is preferably 0.5 to 10 mol, morepreferably 0.5 to 5.0 mol, still more preferably 1 to 2 mol,particularly preferably 1 to 1.1 mol, relative to 1 mol of the compound(11), so as to improve the yield and to reduce the waste.

The reaction in the step (12) may be performed in a solvent in thepresence of a thiazolium salt or a base.

Examples of the thiazolium salt include3-ethyl-5-(2-hydroxyethyl)-4-methylthiazolium bromide and3-benzyl-5-(2-hydroxyethyl)-4-methylthiazolium chloride.

Examples of the base include 1,8-diazabicyclo[5.4.0]-7-undecene andtriethylamine.

The solvent is preferably an organic solvent, more preferably an aproticpolar solvent, still more preferably an alcohol or an ether.

Examples of the alcohol include methanol, ethanol, 1-propanol, andisopropanol.

Examples of the ether include ethyl methyl ether, diethyl ether,monoglyme(ethylene glycol dimethyl ether), diglyme(diethylene glycoldimethyl ether), triglyme(triethylene glycol dimethyl ether),tetrahydrofuran, tetraglyme(tetraethylene glycol dimethyl ether), andcrown ethers (e.g., 15-crown-5, 18-crown-6). Tetrahydrofuran and diethylether are preferred.

The reaction temperature in the step (12) is preferably −78° C. to 150°C., more preferably 0° C. to 100° C., still more preferably 40° C. to60° C., particularly preferably 50° C. to 55° C.

The reaction pressure in the step (12) is preferably 0.1 to 5 MPa, morepreferably 0.1 to 1 MPa.

The reaction duration in the step (12) is preferably 0.1 to 72 hours,more preferably 1 to 48 hours, still more preferably 6 to 10 hours.

The elimination reaction for the leaving group in the step (13) may beperformed using a fluoride ion or an acid. Examples of methods ofeliminating the leaving group include a method of using hydrofluoricacid; a method of using an amine complex of hydrogen fluoride such aspyridine-nHF or triethylamine-nHF; a method of using an inorganic saltsuch as cesium fluoride, potassium fluoride, lithium tetrafluoroborate(LiBF₄), or ammonium fluoride; and a method of using an organic saltsuch as tetrabutylammonium fluoride (TBAF).

The elimination reaction for the leaving group in the step (13) may beperformed in a polar solvent. The solvent is preferably an organicsolvent, more preferably an aprotic polar solvent, still more preferablyan ether.

Examples of the ether include ethyl methyl ether, diethyl ether,monoglyme(ethylene glycol dimethyl ether), diglyme(diethylene glycoldimethyl ether), triglyme(triethylene glycol dimethyl ether),tetrahydrofuran, tetraglyme(tetraethylene glycol dimethyl ether), andcrown ethers (e.g., 15-crown-5, 18-crown-6). Tetrahydrofuran and diethylether are preferred.

The reaction temperature in the step (13) is preferably −78° C. to 150°C., more preferably 0° C. to 100° C., still more preferably 0° C. to 40°C., particularly preferably 0° C. to 20° C.

The reaction pressure in the step (13) is preferably 0.1 to 5 MPa, morepreferably 0.1 to 1 MPa.

The reaction duration in the step (13) is preferably 0.1 to 72 hours,more preferably 1 to 48 hours, still more preferably 3 to 8 hours.

The oxidation in the step (14) may be performed in a solvent in thepresence of sodium chlorite.

The solvent used may be any of alcohols such as methanol, ethanol,1-propanol, isopropanol, 1-butanol, and tert-butyl alcohol and water. Asolution of disodium phosphate may be used as a buffer.

Examples of the alkali used in the step (15) include sodium hydroxide,potassium hydroxide, lithium hydroxide, and ammonia. Ammonia solution ispreferably used.

The resulting compounds may be subjected to any of evaporation of asolvent or operations such as distillation and purification after therespective steps, whereby the purity of each compound may be increased.

The compound of the invention may also favorably be produced by aproduction method including:

a step (21) of reacting a ketone represented by the following formula:

(wherein R³ is defined as mentioned above; R²² is a monovalent organicgroup; and E is a leaving group) and a carboxylate represented by thefollowing formula:

(wherein R¹ is defined as mentioned above; and R²³ is a monovalentorganic group) to provide a compound (21) represented by the followingformula:

(wherein R¹, R³, and E are defined as mentioned above; and R²⁴ is asingle bond or a divalent linking group);

a step (22) of eliminating the leaving group in the compound (21) toprovide a compound (22) represented by the following formula:

(wherein R¹, R²⁴, and R³ are defined as mentioned above);

a step (23) of oxidizing the compound (22) to provide a compound (23)represented by the following formula:

(wherein R¹, R²⁴, and R³ are defined as mentioned above); and

a step (24) of bringing the compound (23) into contact with an alkali toprovide a compound (24) represented by the following formula:

(wherein R¹, R²⁴, R³, and X are defined as mentioned above).

When R¹ contains a furan ring, the furan ring may be cleaved with anacid and converted into a dicarbonyl Acetic acid is preferred.

E represents a leaving group. Examples of the leaving group include atert-butyldimethylsilyl (TBS) group, a triethylsilyl (TES) group, atriisopropylsilyl (TIPS) group, a tert-butyldiphenylsilyl (TBDPS) group,and a benzyl (Bn) group.

R²² is preferably a linear or branched alkyl group containing one ormore carbon atoms, more preferably a methyl group.

R²³ is preferably a linear or branched alkyl group containing one ormore carbon atoms, more preferably a methyl group.

R²⁴ is preferably a linear or branched alkylene group containing one ormore carbon atoms, more preferably a methylene group (—CH₂—).

The reaction in the step (21) may be performed in a solvent in thepresence of a base.

Examples of the base include sodium amide, sodium hydride, sodiummethoxide, and sodium ethoxide.

The solvent is preferably an organic solvent, more preferably an aproticpolar solvent, still more preferably an alcohol or an ether.

Examples of the alcohol include methanol, ethanol, 1-propanol, andisopropanol.

Examples of the ether include ethyl methyl ether, diethyl ether,monoglyme(ethylene glycol dimethyl ether), diglyme(diethylene glycoldimethyl ether), triglyme(triethylene glycol dimethyl ether),tetrahydrofuran, tetraglyme(tetraethylene glycol dimethyl ether), andcrown ethers (e.g., 15-crown-5, 18-crown-6). Tetrahydrofuran and diethylether are preferred.

The reaction temperature in the step (21) is preferably −78° C. to 150°C., more preferably 0° C. to 100° C., still more preferably 0° C. to 40°C., particularly preferably 0° C. to 20° C.

The reaction pressure in the step (21) is preferably 0.1 to 5 MPa, morepreferably 0.1 to 1 MPa.

The reaction duration in the step (21) is preferably 0.1 to 72 hours,more preferably 1 to 48 hours, still more preferably 3 to 8 hours.

The elimination reaction for the leaving group in the step (22) may beperformed using a fluoride ion or an acid. Examples of methods ofeliminating the leaving group include a method of using hydrofluoricacid; a method of using an amine complex of hydrogen fluoride such aspyridine-nHF or triethylamine-nHF; a method of using an inorganic saltsuch as cesium fluoride, potassium fluoride, lithium tetrafluoroborate(LiBF₄), or ammonium fluoride; and a method of using an organic saltsuch as tetrabutylammonium fluoride (TBAF).

The elimination reaction for the leaving group in the step (22) may beperformed in a solvent. The solvent is preferably an organic solvent,more preferably an aprotic polar solvent, still more preferably anether.

Examples of the ether include ethyl methyl ether, diethyl ether,monoglyme(ethylene glycol dimethyl ether), diglyme(diethylene glycoldimethyl ether), triglyme(triethylene glycol dimethyl ether),tetrahydrofuran, tetraglyme(tetraethylene glycol dimethyl ether), andcrown ethers (e.g., 15-crown-5, 18-crown-6). Tetrahydrofuran and diethylether are preferred.

The reaction temperature in the step (22) is preferably −78° C. to 150°C., more preferably 0° C. to 100° C., still more preferably 0° C. to 40°C., particularly preferably 0° C. to 20° C.

The reaction pressure in the step (22) is preferably 0.1 to 5 MPa, morepreferably 0.1 to 1 MPa.

The reaction duration in the step (22) is preferably 0.1 to 72 hours,more preferably 1 to 48 hours, still more preferably 3 to 8 hours.

The oxidation in the step (23) may be performed in a solvent in thepresence of sodium chlorite.

The solvent used may be any of alcohols and water. A solution ofdisodium phosphate may be used as a buffer.

Examples of the alkali used in the step (24) include sodium hydroxide,potassium hydroxide, lithium hydroxide, and ammonia. Ammonia solution ispreferably used.

The resulting compounds may be subjected to any of evaporation of asolvent or operations such as distillation and purification after therespective steps, whereby the purity of each compound may be increased.

The compound of the invention may also favorably be produced by a methodincluding:

a step (31) of reacting an alkyl halide represented by the followingformula:

Y—R³—CH₂—OE

(wherein R³ is defined as mentioned above; Y is a halogen atom; and E isa leaving group) and lithium acetylide represented by the followingformula:

(wherein R¹ is defined as mentioned above) to provide a compound (31)represented by the following formula:

(wherein R¹, R³, and E are defined as mentioned above);

a step (32) of oxidizing the compound (31) to provide a compound (32)represented by the following formula:

(wherein R¹, R³, and E are defined as mentioned above);

a step (33) of eliminating the leaving group in the compound (32) toprovide a compound (33) represented by the following formula:

(wherein R¹ and R³ are defined as mentioned above);

a step (34) of oxidizing the compound (33) to provide a compound (34)represented by the following formula:

(wherein R¹ and R³ are defined as mentioned above); and

a step (35) of bringing the compound (34) into contact with an alkali toprovide a compound (35) represented by the following formula:

(wherein R¹, R³, and X are defined as mentioned above).

When R¹ contains a furan ring, the furan ring may be cleaved with anacid and converted into a dicarbonyl derivative, for example. Examplesof the acid include acetic acid, hydrochloric acid, andp-toluenesulfonic acid. Acetic acid is preferred.

E represents a leaving group. Examples of the leaving group include atert-butyldimethylsilyl (TBS) group, a triethylsilyl (TES) group, atriisopropylsilyl (TIPS) group, a tert-butyldiphenylsilyl (TBDPS) group,and a benzyl (Bn) group.

For the reaction ratio between the alkyl halide and the lithiumacetylide in the step (31), the amount of the lithium acetylide ispreferably 0.5 to 10 mol, more preferably 0.6 to 5.0 mol, still morepreferably 1 to 2 mol, particularly preferably 1 to 1.2 mol, relative to1 mol of the alkyl halide, so as to improve the yield and to reduce thewaste.

The reaction in the step (31) may be performed in a solvent. The solventis preferably hexane.

The reaction temperature in the step (31) is preferably −100° C. to −40°C., more preferably −80° C. to −50° C., while preferably −100° C. to100° C., more preferably −80° C. to 50° C.

The reaction pressure in the step (31) is preferably 0.1 to 5 MPa, morepreferably 0.1 to 1 MPa.

The reaction duration in the step (31) is preferably 0.1 to 72 hours,more preferably 1 to 48 hours, still more preferably 6 to 10 hours.

The oxidation in the step (32) may be performed in a nitrile solventusing a complex generated by treating [(Cn*)Ru^(III)(CF₃CO₂)₃].H₂O(wherein Cn* is 1,4,7-trimethyl-1,4,7-triazabicyclononane) with(NH₄)₂Ce(NO₃)₆ and trifluoroacetic acid and then adding sodiumperchlorate thereto.

After the oxidation is completed, the product may be neutralized with analkali, and then an organic solvent such as an ether may be used toextract the compound (32).

The reaction temperature in the step (32) is preferably −78° C. to 150°C., more preferably 0° C. to 100° C., still more preferably 30° C. to100° C., particularly preferably 40° C. to 90° C.

The reaction pressure in the step (32) is preferably 0.1 to 5 MPa, morepreferably 0.1 to 1 MPa.

The reaction duration in the step (32) is preferably 0.1 to 72 hours,more preferably 1 to 48 hours, still more preferably 3 to 8 hours.

The elimination reaction for the leaving group in the step (33) may beperformed using a fluoride ion or an acid. Examples of methods ofeliminating the leaving group include a method of using hydrofluoricacid; a method of using an amine complex of hydrogen fluoride such aspyridine-nHF or triethylamine-nHF; a method of using an inorganic saltsuch as cesium fluoride, potassium fluoride, lithium tetrafluoroborate(LiBF₄), or ammonium fluoride; and a method of using an organic saltsuch as tetrabutylammonium fluoride (TBAF).

The elimination reaction for the leaving group in the step (33) may beperformed in a solvent. The solvent is preferably an organic solvent,more preferably an aprotic polar solvent, still more preferably anether.

Examples of the ether include ethyl methyl ether, diethyl ether,monoglyme(ethylene glycol dimethyl ether), diglyme(diethylene glycoldimethyl ether), triglyme(triethylene glycol dimethyl ether),tetrahydrofuran, tetraglyme(tetraethylene glycol dimethyl ether), andcrown ethers (e.g., 15-crown-5, 18-crown-6). Tetrahydrofuran and diethylether are preferred.

The reaction temperature in the step (33) is preferably −78° C. to 150°C., more preferably 0° C. to 100° C., still more preferably 0° C. to 40°C., particularly preferably 0° C. to 20° C.

The reaction pressure in the step (33) is preferably 0.1 to 5 MPa, morepreferably 0.1 to 1 MPa.

The reaction duration in the step (33) is preferably 0.1 to 72 hours,more preferably 1 to 48 hours, still more preferably 3 to 8 hours.

The oxidation in the step (34) may be performed in a solvent in thepresence of sodium chlorite.

The solvent used may be any of alcohols and water. A solution ofdisodium phosphate may be used as a buffer.

Examples of the alkali used in the step (35) include sodium hydroxide,potassium hydroxide, lithium hydroxide, and ammonia. Ammonia solution ispreferably used.

The resulting compounds may be subjected to any of evaporation of asolvent or operations such as distillation and purification after therespective steps, whereby the purity of each compound may be increased.

The compound of the invention may also favorably be produced by aproduction method including:

a step (51) of reacting divinyl ketone represented by the followingformula:

and 2-methylfuran represented by the following formula:

to provide a compound (51) represented by the following formula:

a step (52) of reacting the compound (51) and furan represented by thefollowing formula:

to provide a compound (52) represented by the following formula:

a step (53) of heating the compound (52) in the presence of an acid toprovide a compound (53) represented by the following formula:

a step (54) of oxidizing the compound (53) to provide a compound (54)represented by the following formula:

a step (55) of bringing the compound (54) into contact with an alkali toprovide a compound (55) represented by the following formula:

(wherein X is defined as mentioned above).

For the reaction ratio between divinyl ketone and 2-1.0 methylfuran inthe step (51), the amount of 2-methylfuran is preferably 0.5 to 10 mol,more preferably 0.6 to 5.0 mol, still more preferably 0.5 to 1 mol,particularly preferably 0.6 to 0.9 mol, relative to 1 mol of divinylketone, so as to improve the yield and to reduce the waste.

The reaction in the step (51) is preferably performed in the presence ofan acid. Examples of the acid include acetic acid, hydrochloric acid,and p-toluenesulfonic acid. Acetic acid is preferred.

In order to improve the yield and to reduce the waste, the amount of theacid used in the step (51) is preferably 0.1 to 2 mol, more preferably0.1 to 1 mol, relative to 1 mol of divinyl ketone.

The reaction in the step (51) may be performed in a polar solvent. Thesolvent is preferably water or acetonitrile.

The reaction temperature in the step (51) is preferably −78° C. to 150°C., more preferably 0° C. to 100° C., still more preferably 20° C. to100° C., particularly preferably 40° C. to 100° C.

The reaction pressure in the step (51) is preferably 0.1 to 5 MPa, morepreferably 0.1 to 1 MPa.

The reaction duration in the step (51) is preferably 0.1 to 72 hours,more preferably 1 to 48 hours, still more preferably 4 to 8 hours.

For the reaction ratio between the compound (51) and furan in the step(52), the amount of furan is preferably 0.5 to 10 mol, more preferably0.6 to 5.0 mol, still more preferably 1 to 2 mol, particularlypreferably 1 to 1.1 mol, relative to 1 mol of the compound (51), so asto improve the yield and to reduce the waste.

The reaction in the step (52) is preferably performed in the presence ofan acid. Examples of the acid include acetic acid, hydrochloric acid,and p-toluenesulfonic acid. Acetic acid is preferred.

In order to improve the yield and to reduce the waste, the amount of theacid used in the step (52) is preferably 0.1 to 2 mol, more preferably0.1 to 1 mol, relative to 1 mol of the compound (51).

The reaction in the step (52) may be performed in a polar solvent. Thesolvent is preferably water.

The reaction temperature in the step (52) is preferably −78° C. to 150°C., more preferably 0° C. to 100° C., still more preferably 20° C. to100° C., particularly preferably 40° C. to 100° C.

The reaction pressure in the step (52) is preferably 0.1 to 5 MPa, morepreferably 0.1 to 1 MPa.

The reaction duration in the step (52) is preferably 0.1 to 72 hours,more preferably 1 to 48 hours, still more preferably 4 to 8 hours.

In the step (53), the compound (52) is heated in the presence of an acidso that the furan rings are opened.

The acid is preferably hydrochloric acid or sulfuric acid.

The reaction in the step (53) may be performed in a polar solvent. Thesolvent is preferably water.

The reaction temperature in the step (53) is preferably −78° C. to 150°C., more preferably 0° C. to 100° C., still more preferably 50° C. to100° C., particularly preferably 70° C. to 100° C.

The reaction pressure in the step (53) is preferably 0.1 to 5 MPa, morepreferably 0.1 to 1 MPa.

The reaction duration in the step (53) is preferably 0.1 to 72 hours,more preferably 1 to 48 hours, still more preferably 1 to 12 hours.

The oxidation in the step (54) may be performed in a solvent in thepresence of sodium chlorite.

The solvent used may be any of tert-butyl alcohol and water. A solutionof disodium phosphate may be used as a buffer.

Examples of the alkali used in the step (55) include sodium hydroxide,potassium hydroxide, lithium hydroxide, and ammonia. Ammonia solution ispreferably used.

The resulting compounds may be subjected to any of evaporation of asolvent or operations such as distillation and purification after therespective steps, whereby the purity of each compound may be increased.

The compound of the invention may also favorably be produced by aproduction method including:

a step (61) of reacting an alkene represented by the following formula:

(wherein R¹ is defined as mentioned above; and R²¹ is a single bond or adivalent linking group) and an alkyne represented by the followingformula:

(wherein Y⁶¹ is an alkyl ester group) to provide a compound (61)represented by the following formula:

(wherein R¹, R²¹, and Y⁶¹ are defined as mentioned above);

a step (62) of treating the compound (61) with an alkali, and then withan acid to provide a compound (62) represented by the following formula:

(wherein R¹ and R²¹ are defined as mentioned above); and

a step (63) of bringing the compound (62) into contact with an alkali toprovide a compound (63) represented by the following formula:

(wherein R, R²¹, and X are defined as mentioned above).

When R¹ contains a furan ring, the furan ring may be cleaved with anacid and converted into a dicarbonyl derivative, for example. Examplesof the acid include acetic acid, hydrochloric acid, andp-toluenesulfonic acid. Acetic acid is preferred.

R²¹ is preferably a single bond or a linear or branched alkylene groupcontaining one or more carbon atoms.

For the reaction ratio between the alkene and the alkyne in the step(61), the amount of the alkene is preferably 0.5 to 2 mol, morepreferably 0.6 to 1.2 mol, while preferably 0.5 to 10 mol, morepreferably 0.6 to 5.0 mol, relative to 1 mol of the alkyne, so as toimprove the yield and to reduce the waste.

The reaction in the step (61) is preferably performed in the presence ofa metal catalyst. An example of the metal is ruthenium.

In order to improve the yield and to reduce the waste, the amount of themetal catalyst used in the step (61) is preferably 0.00001 to 0.4 mol,more preferably 0.00005 to 0.1 mol, still more preferably 0.01 to 0.4mol, particularly preferably 0.05 to 0.1 mol, relative to 1 mol of thealkene.

The reaction in the step (61) may be performed in a polar solvent. Thesolvent is preferably water, acetonitrile, dimethylacetamide, ordimethylformamide.

The reaction temperature in the step (61) is preferably 20° C. to 160°C., more preferably 40° C. to 140° C.

The reaction pressure in the step (61) is preferably 0.1 to 5 MPa, morepreferably 0.1 to 1 MPa.

The reaction duration in the step (61) is preferably 0.1 to 72 hours,more preferably 1 to 48 hours, still more preferably 4 to 8 hours.

For the reaction ratio between the compound (61) and the alkali in thestep (62), the amount of the alkali is preferably 0.5 to 10 mol, morepreferably 0.6 to 5.0 mol, still more preferably 0.6 to 2 mol,particularly preferably 0.8 to 1.1 mol, relative to 1 mol of thecompound (61), so as to improve the yield and to reduce the waste.

In order to improve the yield and to reduce the waste, the amount of theacid used in the step (62) is preferably 1.0 to 20.0 mol, morepreferably 1.0 to 10.0 mol, relative to 1 mol of the compound (61).

The reaction in the step (62) may be performed in a polar solvent. Thesolvent is preferably water.

The reaction temperature in the step (62) is preferably 0° C. to 100°C., more preferably 20° C. to 100° C.

The reaction pressure in the step (62) is preferably 0.1 to 5 MPa, morepreferably 0.1 to 1 MPa.

The reaction duration in the step (62) is preferably 0.1 to 72 hours,more preferably 1 to 48 hours, still more preferably 4 to 8 hours.

Examples of the alkali used in the step (63) include sodium hydroxide,potassium hydroxide, lithium hydroxide, and ammonia. Ammonia solution ispreferably used.

The resulting compounds may be subjected to any of evaporation of asolvent or operations such as distillation and purification after therespective steps, whereby the purity of each compound may be increased.

EXAMPLES

The invention is described hereinbelow with reference to examples.Still, these examples are not intended to limit the invention.

The parameters in the examples were determined by the following methods.

Example 1

A mixture of lithium (2.0 g), dimethylphenylchlorosilane (8.4 g), andtetrahydrofuran (120 mL) was stirred at room temperature for six hours.To the reaction solution was added4-(tert-butyldimethylsiloxy)-1-morpholinobutan-1-one (10 g), and themixture was stirred at −78° C. for two hours. To the reaction solutionwas added a saturated ammonium chloride aqueous solution (300 mL). Themixture was subjected to extraction with ethyl acetate. The extract wasdried over sodium sulfate and the solvent was evaporated under reducedpressure. The residue was then purified by silica gel columnchromatography. Thereby,4-(tert-butyldimethylsiloxy)-1-(dimethyl(phenyl)silyl)butan-1-one (6.4g) was obtained.

¹H-NMR (CDCl₃) δ ppm: −0.01 (s, 6H), 0.49 (s, 6H), 0.85 (s, 911),1.61-1.71 (m, 2H), 2.66 (J=7.0, t, 2H), 3.51 (J=6.2, t, 2H), 7.38-7.40(m, 3H), 7.53-7.57 (m, 2H)

A mixture of4-(tert-butyldimethylsiloxy)-1-(dimethyl(phenyl)silyl)butan-1-one (6.4g), 1-octen-3-one (2.41 g),3-ethyl-5-(2-hydroxyethyl)-4-methylthiazolium bromide (1.42 g),1,8-diazabicyclo[5.4.0]-7-undecene (0.86 g), isopropanol (3.17 g), andtetrahydrofuran (11.5 mL) was stirred at 75° C. for eight hours. Thesolvent in the reaction solution was evaporated under reduced pressure,and the residue was then purified by silica gel column chromatography.Thereby, 1-tert-butyldimethylsiloxydodecane-4,7-dione (4.0 g) wasobtained.

¹H-NMR (CDCl₃) δ ppm: 0.02 (s, 6H), 0.88 (s, 12H), 1.22-1.31 (m, 4H),1.51-1.59 (m, 2H), 1.72-1.83 (m, 2H), 2.43 (J=7.6, t, 2H), 2.55 (J=7.6,t, 2H), 2.67 (s, 4H), 3.59 (J=5.9, t, 2H)

A mixture of 1-tert-butyldimethylsiloxydodecane-4,7-dione (1.9 g), a 1 Msolution (15 mL) of tetrabutylammonium fluoride in tetrahydrofuran, andtetrahydrofuran (17.5 mL) was stirred at 0° C. for two hours. To thereaction solution was added a saturated ammonium chloride solution (100mL). The mixture was subjected to extraction with ethyl acetate. Theextract was dried over sodium sulfate and the solvent was evaporatedunder reduced pressure. The residue was then purified by silica gelcolumn chromatography. Thereby, 1-hydroxydodecane-4,7-dione (2.0 g) wasobtained.

¹H-NMR (CDCl₃) δ ppm: 0.89 (s, 3H), 1.24-1.33 (m, 4H), 1.52-1.58 (m,2H), 1.81-1.90 (m, 2H), 2.45 (J=7.6, t, 2H), 2.63 (J=7.0, t, 2H), 2.76(s, 4H), 3.65 (J=5.9, t, 2H)

A mixture of 2,2,6,6-tetramethylpiperidine-1-oxyl,1-hydroxydodexane-4,7-dione, potassium bromide, sodium hypochlorite,sodium hydrogen carbonate, sodium carbonate, and dichloromethane wasstirred at 25° C. for one hour. After the reaction, methanol was addedthereto. The aqueous phase was extracted with dichloromethane (50 mL)three times. The extract was washed with saturated brine, and then theorganic phase was dried. Thereby, 4,7-dioxododecanal was obtained.

A solution mixture of 4,7-dioxododecanal, 2-methyl-2-butene, tBuOH,water, a Na₂HPOO₄ solution, and NaClO₂ was stirred at 25° C. for onehour. Brine was added to the solution mixture, and the mixture wassubjected to extraction with chloroform four times. The organic phasewas dried over sodium sulfate and concentrated. The residue was thenpurified by silica gel column chromatography (hexane:ethyl acetate).Thereby, 4,7-dioxododecanoic acid was obtained.

Then, 4,7-dioxododecanoic acid was added to 30% ammonia water and waterwas evaporated. Thereby, ammonium 4,7-dioxododecanoate was obtained.

Example 2

Divinyl ketone (7.4 g), 2-methylfuran (8.0 g), acetic acid (6 mL), andwater (60 mL) were stirred at 40° C. for four hours. The reactionsolution was added to a saturated sodium hydrogen carbonate solution.The mixture was subjected to extraction with ethyl acetate. The extractwas dried over sodium sulfate and the solvent was evaporated underreduced pressure. The residue was then purified by silica gel columnchromatography (hexane:ethyl acetate=25:1). Thereby,1-(5-methyl-2-furanyl)-3-buten-2-one (7.4 g) was obtained.

¹H-NMR (CDCl₃) δ ppm: 5.88 (dd, J=17.4, 10.6, 2H), 6.32 (dd, J=17.4,1.3, 2H), 5.88 (dd, J=10.6, 1.3, 2H)

Then, 1-(5-methyl-2-furanyl)-3-buten-2-one (1.0 g), furan (4 g), aceticacid (0.4 mL), and water (4 mL) were stirred at 100° C. for 24 hours.The reaction solution was added to a saturated sodium hydrogen carbonatesolution and the mixture was subjected to extraction with ethyl acetate.The extract was dried over sodium sulfate and the solvent was evaporatedunder reduced pressure. The residue was then purified by silica gelcolumn chromatography (hexane:ethyl acetate=25:1). Thereby,1-(furan-2-yl)-5-(5-methylfuran-2-yl)pentan-3-one (0.5 g) was obtained.

A mixture of sodium 9-(5-methylfuran-2-yl)-4,7-dioxononyl)sulfate,water, and 1 M hydrochloric acid was stirred at 100° C. for one hour. A10% NaHCO₃ aqueous solution was added to the reaction solution forneutralization. The neutralized solution was subjected to extractionwith ethyl acetate. The extract was dried over sodium sulfate and thesolvent was evaporated under reduced pressure. The residue was thenpurified by silica gel column chromatography (hexane:ethyl acetate=1:1).Thereby, 4,7,10,13-tetraoxotetradecanal was obtained.

A solution mixture of 4,7,10,13-tetraoxotetradecanal, 2-methyl-2-butene,tBuOH, water, a Na₂HPO₄ solution, and NaClO₂ was stirred at 25° C. forone hour. Brine was added to the solution mixture, and the mixture wassubjected to extraction with chloroform four times. The organic phasewas dried over sodium sulfate and concentrated. The residue was thenpurified by silica gel column chromatography (hexane:ethyl acetate).Thereby, 4,7,10,13-tetraoxotetradecanoic acid was obtained.

Then, 4,7,10,13-tetraoxotetradecanoic acid was added to ammonia waterand water was evaporated. Thereby, ammonium4,7,10,13-tetraoxotetradecanoate was obtained.

EXPERIMENTAL EXAMPLE

Each of the compounds obtained in Examples 1 and 2 was dissolved inwater so as to give the concentration shown in Table 1, and the surfacetension was determined by the Wilhelmy method at 20° C. The results areshown in Table 1.

TABLE 1 Amount of compound relative to water (wt %) 0.01 0.1 1 SurfaceExample 1 72.1 62.6 43.4 tension Example 2 73.4 70.2 63 (mN/m)

INDUSTRIAL APPLICABILITY

The compound of the invention can favorably reduce the surface tensionof water.

The compound of the invention can suitably be used as a surfactant.

The compound of the invention can suitably be used as a surfactantpromoter (in particular, a surfactant promoter for agents such ascoating material, lacquer, and adhesive).

The compound of the invention can suitably be used as a viscosityreducing agent, for example.

The compound of the invention can suitably be used as a dispersant, inparticular an aqueous dispersant, for example.

The compound of the invention can suitably be used as an emulsifier, forexample.

1. A compound represented by the following formula:

wherein R¹ is a linear or branched alkyl group containing one or morecarbon atoms or a cyclic alkyl group containing three or more carbonatoms, with a hydrogen atom that binds to a carbon atom being optionallyreplaced by a hydroxy group or a monovalent organic group containing anester bond, the alkyl group optionally containing a carbonyl group whencontaining two or more carbon atoms, and the alkyl group optionallycontaining a monovalent or divalent heterocycle or being optionally in acyclized form when containing three or more carbon atoms; R² and R³ areeach individually a single bond or a divalent linking group; R¹, R², andR³ contain five or more carbon atoms in total; A is —COOX or —SO₃X,wherein X is H, a metal atom, NR⁴ ₄, imidazolium optionally containing asubstituent, pyridinium optionally containing a substituent, orphosphonium optionally containing a substituent, where R⁴s are each H oran organic group and are the same as or different from each other; andany two of R¹, R², and R³ optionally bind to each other to form a ring.2. The compound according to claim 1, wherein in the formula, R² and R³are each individually a single bond, a linear or branched alkylene groupcontaining one or more carbon atoms, or a cyclic alkylene groupcontaining three or more carbon atoms, with a hydrogen atom that bindsto a carbon atom being optionally replaced by a hydroxy group or amonovalent organic group containing an ester bond.
 3. The compoundaccording to claim 1, wherein in the formula, R¹ is a C1-C8 linear orbranched alkyl group containing no carbonyl group, a C3-C8 cyclic alkylgroup containing no carbonyl group, a C2-C45 linear or branched alkylgroup containing 1 to 10 carbonyl groups, a C3-C45 cyclic alkyl groupcontaining a carbonyl group, or a C3-C45 alkyl group containing amonovalent or divalent heterocycle.
 4. The compound according to claim1, wherein in the formula, R¹ is a group represented by the followingformula:

wherein n11 is an integer of 0 to 10; R¹¹ is a C1-C5 linear or branchedalkyl group or a C3-C5 cyclic alkyl group; and R¹² is a C0-C3 alkylenegroup, and when n11 is an integer of 2 to 10, R¹²s are the same as ordifferent from each other.
 5. The compound according to claim 1, whereinin the formula, R² and R³ are each individually a linear or branchedalkylene group containing no carbonyl group and containing one or morecarbon atoms.
 6. The compound according to claim 1, wherein in theformula, R² and R³ are each individually a C1-C3 linear or branchedalkylene group containing no carbonyl group.
 7. The compound accordingto claim 1, wherein in the formula, X is NH₄.
 8. A surfactant comprisingthe compound according to claim
 1. 9. An aqueous dispersant comprisingthe compound according to claim 1.